CN107792848A - The method that synchronizing ultrasound chemistry prepares functionalization graphene with mechanochemical reaction - Google Patents
The method that synchronizing ultrasound chemistry prepares functionalization graphene with mechanochemical reaction Download PDFInfo
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Abstract
The invention discloses the method that a kind of synchronizing ultrasound chemistry prepares functionalization graphene with mechanochemical reaction.By the way that graphite raw material and functionalized reagent are added in ultrasonic ball-grinding machine, with 100~500rpm rotating speed ultrasound 1~72h of ball milling under ultrasonic environment, the functionalization graphene containing functional group is obtained.This method peels off graphite using synchronizing ultrasound ball milling and obtains graphene, and by sonochemistry, mechanochemical treatment, functionalized reagent is set quickly to be chemically reacted with graphene, the functional modification to graphene is realized simultaneously, effectively improve the charge stripping efficiency and its dispersion stabilization of graphene, regulate and control the structure and performance of grapheme material, extend its application field.
Description
Technical field
The present invention relates to a kind of method for preparing functionalization graphene, particularly relates to a kind of based on synchronizing ultrasound chemistry and machine
The method that tool chemical method prepares functionalization graphene.
Background technology
Graphene has excellent electricity and mechanical property, and in recent years as the focus of research field, graphene is 2004
Year successfully prepares in the method for mechanical stripping, and obtains Nobel Prize in physics in 2010.Graphene is as one
The carbon two dimensional crystal of individual atom number of plies thickness, there is the excellent performances such as high conductivity, high-specific surface area, high intensity.
At present it has been reported that the graphene method for preparing be mainly chemical vapour deposition technique, mechanical stripping, oxidation-reduction method
Deng.Wherein chemical gaseous phase depositing process preparation efficiency is relatively low, it is difficult to realizes prepared by magnanimity, it is often more important that the graphene of preparation is not
Containing functional group, exist mostly with film morphology, seriously hinder the further dispersion processing of graphene with utilizing.Oxidation-reduction method
Graphene oxide can be prepared with magnanimity, but danger is brought to preparation process using substantial amounts of acid and strong oxidizer in preparation process
Danger and pollution, and the functional group of obtained graphene oxide is too many, reduces the electrical and thermal conductivity performance of graphene oxide.Machinery
The easy magnanimity of stripping method peels off preparing graphite alkene, but efficient low, low yield, without functional group, easily reunite the defects of, and
And it is few containing functional group, application field is limited.
Sonochemistry is to accelerate and improve a new methods of reaction yield using ultrasonic energy, and its cardinal principle is super
Sound cavitation effect caused by sound wave be the formation of liquid hollow chamber, vibration, growth shrink and avalanche caused by some row chemistry and
Physical change can promote chemical reaction to carry out.Sonochemistry process is to concentrate energy and the process that discharges rapidly, process cavitation
More than 5000K high temperature and 5.05 × 10 can be produced by steeping during avalanche8Pa high pressure, velocity variations are up to 1010K/s, and with production
Raw strong shock wave and speed per hour are up to 400Km microjet, and this just to be not easy the chemical reaction realized under general condition, is carried
New special chemical physical environment has been supplied, new chemical reaction passage has been opened, improves reaction efficiency.Chinese invention patent
The in-situ composite that CN201310058605.1 prepares zinc manganate and graphene oxide by sonochemistry hydro-thermal method, obtain
Height ratio capacity lithium ion battery negative material.It is noted that the patent is not grapheme modified using sonochemistry.Middle promulgated by the State Council
Bright patent CN201510492361.7 sonochemical methods synthesizing magnetic Kaempferol microballoon, then by itself and amination graphene quantum
Point is compound to obtain magnetic coupling pharmaceutical carrier.
The peculiar Environmental Chemistry environment that mechanochemistry is created can effectively arousal function reagent produce it is efficient grapheme modified.In
State patent of invention CN201510335466.1 is by containing the molecule and inorganic semiconductor nanometer material for being conjugated big pi bond, by certain matter
Amount ratio is well mixed, and under certain ball/material ratio, is added in the ball grinder of high-energy ball milling, under appropriate rotational speed of ball-mill,
Certain time is handled, obtains the conductor photocatalysis material of conjugated molecule hydridization.The invention has that technological process is simple, operation letter
Just, without using solvent, post processing is simple, low manufacture cost, and the composite catalyzing material activity being prepared is high, is adapted to batch to prepare
Conjugated molecule hybrid modification conductor photocatalysis material.But the patent is not grapheme modified using mechanochemistry, is allowed to band
On, functional group.
In summary, at present, while functionalization graphene is prepared with sonochemistry and mechanochemistry not to be reported also.
The content of the invention
Functionalization graphene is prepared with mechanochemical reaction based on synchronizing ultrasound chemistry it is an object of the invention to provide one kind
Method strategy.
To achieve the above object, synchronizing ultrasound chemistry provided by the present invention prepares functionalization graphene with mechanochemical reaction
Method, comprise the following steps：
1) graphite raw material and functionalized reagent are mixed, added in ultrasonic ball-grinding machine, with 100 under ultrasonic environment
1~72h of~500rpm rotating speed ultrasound ball millings；
2) ultrasonic ball milling product obtains containing functional group by purifying and (dialysing in such as solvent washing or bag filter), dry
Functionalization graphene.
This method uses sonochemistry and mechanochemistry arousal function reagent functionalization graphene simultaneously, can provide special change
Physical environment is learned, makes chemical reaction efficiency and yield higher, can more obtain the functionalization graphene of favorable dispersibility, while ultrasound
Chemistry can be effectively peeled off graphite into graphene with mechanochemical process so that stripping synchronously completes with modification, improves preparation effect
Rate.
Preferably, being added in step 1), before ultrasonic ball milling or in ultrasonic mechanical milling process also into mixture has stripping molten
Agent, it is described stripping solvent include water, ethanol, DMF, 1-METHYLPYRROLIDONE, one kind in ionic liquid or
A variety of mixed solvents, or the ionic liquid-filler shear thickening system formed by ionic liquid and filler configuration.
Preferably, the cation composition of the ionic liquid includes glyoxaline cation, pyridylium, quaternary ammonium salt cationic
With the one or more in quaternary phosphonium salt cation, the anion composition of the ionic liquid includes tetrafluoro boric acid salt anionic, six
One or more in fluorophosphate anion, chlorion, bromide ion, trifluoroacetic acid anion, trifluoromethanesulfonic acid anion.
Preferably, the filler includes silica, aluminum oxide, magnesia, zinc oxide, nickel oxide, cupric oxide, oxidation
One or more in beryllium, carbon ball, polymer microballoon and CNT, the size of the filler is 1nm~100 μm.
Preferably, the ultrasonic ball milling is carried out under vacuum environment or inert gas environment (such as inflated with nitrogen or argon gas),
Vacuum or inert gas environment are advantageous to free radical isoreactivity species caused by ultrasonic ball milling functional mass and graphite alkene reaction.
Preferably, the graphite raw material includes native graphite, artificial synthesized graphite, expanded graphite, fluorographite and oxygen
One or more in graphite.
Preferably, the functionalized reagent is the material for making graphene ribbon polar functionalities group, including azo dimethyl-
The double hydroxyls of N-2- hydroxyl butyl propionamides (VA-086), oxalic acid, ammonium oxalate, sodium oxalate, sodium bioxalate, sodium carbonate, azo dimethyl-N-
Dimethyl hydroxyethyl propionamide (VA-080), the isobutyl imidazoline hydrochloride (VA-50) of azo two, the isobutyl imidazoline hydrochloride of azo two
(VA-044) ,-N- hydroxyisobutyl amidine hydrates (VA-057) of azo two, azo two-N, N- cyclobutyl isobutyl amidine hydrate,
One kind in N- methyl aminoacetic acids, sodium acid carbonate, ammonium carbonate, ammonium hydrogen carbonate, ammonium hydrogen sulfate, ammonium persulfate and organic carbonate
Or a variety of mixture.
Preferably, the functionalized reagent is the material for making the nonpolar functionalization group of graphene ribbon, including nitrous acid is different
Pentyl ester, natrium nitrosum, cumidine, halogenated alkane, alchlor, ferric trichloride, potassium, n-butanol, isopropanol, ethanol,
Propyl alcohol, butanol, octanol, amylalcohol, hexanol, enanthol, certain herbaceous plants with big flowers alcohol, ethylene glycol, glycerine, propane diols, anthracene, 9,10- dimethylanthracenes, and five
Benzene, naphthalene [2,3- α] pyrene, formaldehyde, 2,3- benzodiazines, a-amino acid, polyformaldehyde, bromobenzene, one kind in bromonaphthalene and cylite or
A variety of mixtures.
The beneficial effects of the invention are as follows：This method prepares functionalization graphene using the ultrasound under same space-time with ball milling,
Again by the synergistic function of ball milling Strong shear while graphite raw material is acted on by the loosening of ultrasonic wave, make graphite layers
By ball milling Strong shear power while loosening, it is more easy to obtain the scattered functionalization graphene of energy high concentration, high stable.This method work
Skill is unique, and mild condition, cost is controllable, is adapted to the scattered functionalization graphene of a large amount of preparation high concentrations, high stable.
Brief description of the drawings
Fig. 1~3 are respectively the transmission electron microscope photo of few layer function graphite alkene made from embodiment 1,2,5.
Fig. 4 is dividing for the graphene that functionalization graphene (right side) made from embodiment 4 is peeled off to obtain with usual vehicle ball milling
The situation of dissipating contrast photo.
Embodiment
The method provided by the present invention that functionalization graphene is prepared with mechanochemical reaction based on synchronizing ultrasound chemistry, including
Following steps：
1) by graphite raw material, functionalized reagent and peel off solvent and mix, add in ultrasonic ball-grinding machine, in vacuum or
Under atmosphere of inert gases, and ultrasonic environment, with 100~500rpm rotating speed ultrasound ball millings, 1~72h；
2) ultrasonic ball milling product by purifying, dry, obtain the functionalization graphene containing functional group.
The stripping solvent is included in water, ethanol, N,N-dimethylformamide, 1-METHYLPYRROLIDONE, ionic liquid
One or more mixed solvents, or the ionic liquid-filler shear thickening system formed by ionic liquid and filler configuration.
Wherein：
The cation composition of ionic liquid includes glyoxaline cation, pyridylium, quaternary ammonium salt cationic and quaternary alkylphosphonium salt sun
One or more in ion, the anion composition of the ionic liquid include tetrafluoro boric acid salt anionic, hexafluorophosphate the moon
One or more in ion, chlorion, bromide ion, trifluoroacetic acid anion, trifluoromethanesulfonic acid anion.
Filler includes silica, aluminum oxide, magnesia, zinc oxide, nickel oxide, cupric oxide, beryllium oxide, carbon ball, polymerization
One or more in thing microballoon and CNT, the size of the filler is 1nm~100 μm.
Graphite raw material includes one in native graphite, artificial synthesized graphite, expanded graphite, fluorographite and graphite oxide
Kind is a variety of.
According to the polarity of obtained functionalization graphene, functionalized reagent can be divided into two kinds, and one kind is to make graphene ribbon
The material of polar functionalities group, including azo dimethyl-N -2- hydroxyl butyl propionamide, oxalic acid, ammonium oxalate, sodium oxalate, oxalic acid
The double hydroxymethylhydroxyethyl propionamides of hydrogen sodium, sodium carbonate, azo dimethyl-N-, the isobutyl imidazoline hydrochloride of azo two, azo two are different
Butamisole quinoline the hydrochloride ,-N- hydroxyisobutyl amidines hydrate of azo two, azo two-N, N- cyclobutyl isobutyl amidine hydrate, carbon
One or more mixtures in sour hydrogen sodium, ammonium carbonate, ammonium hydrogen carbonate, ammonium hydrogen sulfate, ammonium persulfate and organic carbonate.Separately
A kind of is the material for making the nonpolar functionalization group of graphene ribbon, including isoamyl nitrite, natrium nitrosum, cumic aldehyde
Amine, halogenated alkane, alchlor, ferric trichloride, potassium, n-butanol, isopropanol, ethanol, propyl alcohol, butanol, octanol, amylalcohol, hexanol,
Enanthol, certain herbaceous plants with big flowers alcohol, ethylene glycol, glycerine, propane diols, anthracene, 9,10- dimethylanthracenes, pentacene, naphthalene [2,3- α] pyrene, formaldehyde, 2,3-
Benzodiazine, a-amino acid, polyformaldehyde, bromobenzene, one or more mixtures in bromonaphthalene and cylite.
Below by specific embodiment, the present invention is described in further detail.
Embodiment 1
At room temperature, 1g natural graphite powders are mixed with 6g VA-080, adds 25g 1- methyl -3- ethyl imidazol(e) tetrafluoros
Borate, vacuumize, then the vacuum ultrasonic ball milling 8h under 250rpm rotating speed, cooling, mixture wash through ethanol, water washing,
60 DEG C of drying, obtain hydroxy functional groups graphene.
Embodiment 2
At room temperature, by 1g native graphites and 20g ethyl carbonates, then the vacuum ultrasonic ball milling 12h under 350rpm rotating speed, it is cold
But, mixture washs through ethanol, water washing, 60 DEG C of drying, obtains graphene containing carboxyl functional group.
Embodiment 3
At room temperature, by 1g Delaniums, 3g VA-086,15g 1- methyl -3- ethyl imidazol(e) hexafluorophosphates, vacuumize,
The vacuum ultrasonic ball milling 12h under 350rpm rotating speed again, cooling, mixture wash through ethanol, water washing, 60 DEG C of drying, obtain
Hydroxy functional groups graphene.
Embodiment 4
At room temperature, 3g native graphites are mixed with 15g ammonium oxalate, adds 50g 1- methyl -3- ethyl imidazol(e) tetrafluoro boron
Hydrochlorate vacuumizes, then the vacuum ultrasonic ball milling 8h under 250rpm rotating speed, and cooling, mixture washs through ethanol, water washing, 60 DEG C
Drying, obtains graphene containing carboxyl functional group.
Embodiment 5
At room temperature, 1g Delaniums are mixed with 15g VA-057, adds 15g 1- methyl -3- ethyl imidazol(e) hexafluorophosphoric acids
Salt vacuumizes, then the vacuum ultrasonic ball milling 8h under 250rpm rotating speed, and cooling, mixture washs through ethanol, water washing, 60 DEG C of bakings
It is dry, obtain graphene containing carboxyl functional group.
Embodiment 6
At room temperature, by 1g natural graphite powders and 15g formaldehyde, 36g N- methyl aminoacetic acids, vacuumize, then 250rpm's
Vacuum ultrasonic ball milling 8h under rotating speed, cooling, mixture wash through DMF, water washing, 60 DEG C of drying, are contained
N- methyl functionalization graphenes.
Embodiment 7
At room temperature, by 1g natural graphite powders and 5g pentacenes, vacuumize, then the vacuum ultrasonic ball milling under 250rpm rotating speed
8h, cooling, mixture wash through DMF, ethanol washing, 60 DEG C of drying, obtain pentacene function graphite
Alkene.
Embodiment 8
At room temperature, by 1g natural graphite powders and 9,10- dimethylanthracene 8g, vacuumize, then the vacuum under 250rpm rotating speed
Ultrasonic ball milling 8h, cooling, mixture wash through DMF, ethanol washing, 60 DEG C of drying, obtain 9,10- diformazans
Base anthracene functionalization graphene.
Embodiment 9
At room temperature, by 1g natural graphite powders and 2,3- benzodiazine 10g, vacuumize, then the vacuum under 250rpm rotating speed
Ultrasonic ball milling 8h, cooling, mixture wash through DMF, ethanol washing, 60 DEG C of drying, obtain 2,3- diazas
Naphthalene functionalization graphene.
Embodiment 10
Nano silicon 30g is taken, is added in the methyl tetrafluoroborate of 30mL 1- hydroxyethyl imidazoles -3, ultrasonic disperse 1h,
1g graphite is added, vacuum ultrasonic ball milling 8h under 5g VA-080,250rpm rotating speed, cooling, mixture is through N, N- dimethyl formyls
Amine washs, hydrofluoric acid wash, ethanol washing, 60 DEG C of drying, obtains hydroxy functionalized graphene.
Reference examples 1
At room temperature, 1g natural graphite powders are mixed with 6g VA-080, adds 25g 1- methyl -3- ethyl imidazol(e) tetrafluoros
Borate, vacuumize, then washed under general milling equipment with 250rpm rotating speed ball milling 8h, cooling, mixture through ethanol, water
Washing, 60 DEG C of drying, obtains graphene containing functional group.
Reference examples 2
At room temperature, by 1g native graphites and 20g ethyl carbonates, then with 350rpm rotating speed ball milling under general milling equipment
12h, cooling, mixture wash through ethanol, water washing, 60 DEG C of drying, obtain graphene containing functional group.
Reference examples 3
At room temperature, by 1g Delaniums, 3g VA-086,15g 1- methyl -3- ethyl imidazol(e) hexafluoro hexafluorophosphates, take out
Vacuum, then washed under general milling equipment with 350rpm rotating speed ball milling 12h, cooling, mixture through ethanol, water washing, 60
DEG C drying, obtain hydroxy functional groups graphene.
Interpretation of result
To the individual layer rate of the functionalization graphene prepared by each embodiment, reference examples, and in DMF (N, N- dimethyl methyls
Acid amides) dispersion concentration in solvent is detected, and is contrasted with the dispersion concentration disclosed in document, and the results are shown in Table 1.
Obtained graphene Contrast on effect in 1 each embodiment of table, reference examples and document
As shown above, the functionalization graphene prepared by each embodiment, dispersion concentration in DMF solvent for 9.6~
11.7mg/mL, individual layer rate are that the mass percent that individual layer functionalization graphene accounts for repertoire graphite alkene is 13~18%.And
In reference examples, functionalization graphene dispersion concentration is 0.02~0.8mg/mL, and functionalization graphene individual layer rate is 1.6~2.6%；
Graphene dispersion concentration described in bibliography is 0.01~0.2mg/mL.Contrast understands that functionalization graphene of the present invention exists
Dispersion concentration, individual layer rate in DMF solution are far above reference examples and bibliography, are adapted to a large amount of preparation high concentrations, high stable
Scattered functionalization graphene.
The transmitted electron for the graphite ene product that Fig. 1, Fig. 2, Fig. 3 are embodiment 1, embodiment 2, embodiment 5 are prepared shows
Micro mirror photo.It can be seen that from photo：Embodiment 1, embodiment 2, embodiment 5 prepare all into translucent, structural integrity,
The number of plies is less.
Fig. 4 is that the obtained functionalization graphene (right side) containing functional group of embodiment 4 peels off what is obtained with usual vehicle ball milling
Graphene (left side) is in the aqueous solution, the photo after standing 15 days., it is apparent that function fossil in embodiment 4 from photo
The dispersion stabilization of black alkene in aqueous is good, not stratified after standing 15 days, and usual vehicle ball milling peels off obtained graphene
Dispersion stabilization is poor, is layered completely after standing 15 days.
Claims (8)
1. a kind of method that synchronizing ultrasound chemistry prepares functionalization graphene with mechanochemical reaction, it is characterised in that：Including as follows
Step：
1) graphite raw material and functionalized reagent are mixed, added in ultrasonic ball-grinding machine, under ultrasonic environment with 100~
1~72h of 500rpm rotating speed ultrasound ball millings；
2) ultrasonic ball milling product by purifying, dry, obtain the functionalization graphene containing functional group.
2. the method that synchronizing ultrasound chemistry according to claim 1 prepares functionalization graphene with mechanochemical reaction, it is special
Sign is：Being added in step 1), before ultrasonic ball milling or in ultrasonic mechanical milling process also into mixture has stripping solvent, the stripping
Exsolution agent includes water, ethanol, N,N-dimethylformamide, 1-METHYLPYRROLIDONE, one or more mixed in ionic liquid
Bonding solvent, or the ionic liquid-filler shear thickening system formed by ionic liquid and filler configuration.
3. the method that synchronizing ultrasound chemistry according to claim 2 prepares functionalization graphene with mechanochemical reaction, it is special
Sign is：The cation of the ionic liquid include glyoxaline cation, pyridylium, quaternary ammonium salt cationic and quaternary alkylphosphonium salt sun from
One or more in son, the anion of the ionic liquid include tetrafluoro boric acid salt anionic, hexafluorophosphoric acid salt anionic, chlorine
One or more in ion, bromide ion, trifluoroacetic acid anion, trifluoromethanesulfonic acid anion.
4. the method that synchronizing ultrasound chemistry according to claim 2 prepares functionalization graphene with mechanochemical reaction, it is special
Sign is：The filler includes silica, aluminum oxide, magnesia, zinc oxide, nickel oxide, cupric oxide, beryllium oxide, carbon ball, poly-
One or more in compound microballoon and CNT, the size of the filler is 1nm~100 μm.
5. the method that synchronizing ultrasound chemistry according to claim 1 prepares functionalization graphene with mechanochemical reaction, it is special
Sign is：The graphite raw material is included in native graphite, artificial synthesized graphite, expanded graphite, fluorographite and graphite oxide
One or more.
6. functionalization graphene is prepared with mechanochemical reaction according to synchronizing ultrasound according to any one of claims 1 to 5 chemistry
Method, it is characterised in that：The functionalized reagent is the material for making graphene ribbon polar functionalities group, including azo diformazan
The double methylols of base-N-2- hydroxyl butyl propionamide, oxalic acid, ammonium oxalate, sodium oxalate, sodium bioxalate, sodium carbonate, azo dimethyl-N-
Ethoxy propionamide, the isobutyl imidazoline hydrochloride of azo two, the isobutyl imidazoline hydrochloride of the azo two ,-N- hydroxy-isobutyrics of azo two
Base amidine hydrate, azo two-N, N- cyclobutyl isobutyl amidine hydrate, N- methyl aminoacetic acids, sodium acid carbonate, ammonium carbonate, carbon
One or more mixtures in sour hydrogen ammonium, ammonium hydrogen sulfate, ammonium persulfate and organic carbonate.
7. functionalization graphene is prepared with mechanochemical reaction according to synchronizing ultrasound according to any one of claims 1 to 5 chemistry
Method, it is characterised in that：The functionalized reagent is the material for making the nonpolar functionalization group of graphene ribbon, including nitrous acid
Isopentyl ester, natrium nitrosum, cumidine, halogenated alkane, alchlor, ferric trichloride, potassium, n-butanol, isopropanol, second
Alcohol, propyl alcohol, butanol, octanol, amylalcohol, hexanol, enanthol, certain herbaceous plants with big flowers alcohol, ethylene glycol, glycerine, propane diols, anthracene, 9,10- dimethylanthracenes,
Pentacene, naphthalene [2,3- α] pyrene, formaldehyde, 2,3- benzodiazines, a-amino acid, polyformaldehyde, bromobenzene, one in bromonaphthalene and cylite
Kind or a variety of mixtures.
8. functionalization graphene is prepared with mechanochemical reaction according to synchronizing ultrasound according to any one of claims 1 to 5 chemistry
Method, it is characterised in that：The ultrasonic ball milling is carried out under vacuum environment or inert gas environment.
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| CN108910954B (en) * | 2018-06-21 | 2020-07-28 | 广东工业大学 | Two-dimensional material and stripping method and application thereof |
| CN108910954A (en) * | 2018-06-21 | 2018-11-30 | 广东工业大学 | A kind of two-dimensional material and its stripping means and application |
| CN108584933A (en) * | 2018-07-15 | 2018-09-28 | 石梦成 | A kind of fluorinated graphene prepared by ionic liquid stripping |
| CN109148863A (en) * | 2018-09-03 | 2019-01-04 | 新奥石墨烯技术有限公司 | lithium titanate-graphene composite material and its preparation method and application |
| CN109148863B (en) * | 2018-09-03 | 2021-11-19 | 新奥石墨烯技术有限公司 | Lithium titanate-graphene composite material and preparation method and application thereof |
| CN108946715A (en) * | 2018-09-28 | 2018-12-07 | 嘉兴烯成新材料有限公司 | Water soluble starter prepares graphene oxide method |
| CN109231188A (en) * | 2018-11-26 | 2019-01-18 | 上海应用技术大学 | A method of nitrating fluorinated graphene is prepared using fluorographite |
| CN109279600A (en) * | 2018-11-28 | 2019-01-29 | 北京化工大学 | It is a kind of to adulterate carbon material and its preparation method and application more |
| CN109704320A (en) * | 2018-12-28 | 2019-05-03 | 新奥石墨烯技术有限公司 | Functional carbon material and preparation method thereof, dispersion liquid and its application |
| CN112500727B (en) * | 2020-11-20 | 2021-09-17 | 厦门大学 | Weather-resistant paint containing graphene-based composite material and preparation method thereof |
| CN112500727A (en) * | 2020-11-20 | 2021-03-16 | 厦门大学 | Weather-resistant paint containing graphene-based composite material and preparation method thereof |
| CN112408370A (en) * | 2020-12-11 | 2021-02-26 | 中国科学院兰州化学物理研究所 | Preparation method of graphene additive for industrial lubricating oil |
| CN112758919A (en) * | 2020-12-28 | 2021-05-07 | 西安交通大学 | Nitrogen and sulfur double-doped graphene, preparation method thereof and method for preparing supercapacitor material by using same |
| CN114368745A (en) * | 2021-09-17 | 2022-04-19 | 浙江理工大学上虞工业技术研究院有限公司 | Graphene oxide, preparation method and application |
| CN114368745B (en) * | 2021-09-17 | 2023-11-10 | 浙江理工大学上虞工业技术研究院有限公司 | Graphene oxide, preparation method and application |
| CN113941120A (en) * | 2021-12-20 | 2022-01-18 | 河北化工医药职业技术学院 | Digestion method of graphene material |
| CN115285985A (en) * | 2022-10-10 | 2022-11-04 | 深圳华烯新材料有限公司 | Preparation method of carboxylated graphene and carboxylated graphene prepared by same |
| CN115285985B (en) * | 2022-10-10 | 2022-12-06 | 深圳华烯新材料有限公司 | Preparation method of carboxylated graphene and carboxylated graphene prepared by same |
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